Water-soluble phthalocyanine reactive dyestuffs containing an ethylsulfonyl substituent

ABSTRACT

Phthalocycanine reactive dyestuffs corresponding to the formula   wherein Pc represents the radical of a phthalocyanine, R1 and R2 are hydrogen, or identical or different alkyl radicals which may be cyclized and/or further substituted, or they are optionally substituted cycloalkyl, aralkyl or aryl radicals; R3 represents hydrogen, an alkyl radical with 1-5 carbon atoms, which may be substituted by water-solubilizing or by not water-solubilizing groups, or a cycloalkyl radical; R4 and R5 are hydrogen or lower alkyl radicals; A is hydrogen or a substituent; Y is the group SO2-CH2-CH2-OSO3H, -SO2-CH CH2, -SO2-CH2-CH2-S-SO3H; a is a number from 0 to 3, b is a number from 0 to 2, and c is a number from 1 to 4, the sum total of a, b, and c not exceeding 4. The dyestuffs of this invention are useful in dyeing wool, silk, leather, linear polyamides and particularly cellulose, containing fibrous materials such as linen, regenerated cellulose, and cotton.

United States Patent [191 Horst Aug. 12, 1975 [75] Inventor:

[73] Assignee: Bayer Aktieng'esellschaft,

Leverkusen-Bayerwerk, Germany 22 Filed: Dec. 31, 1969 21 Appl. No.: 889,672

Jager Horst, Cologne, Germany [30] Foreign Application Priority Data Jan. 10, 1969 Germany 1901041 [56] References Cited UNITED STATES PATENTS 10/1970 Rudolf et a1. 260/314.5

OTHER PUBLICATIONS The Ring Index (2nd ed.) Patterson et al. (1960) p.

1196. Phthalocyanine Compounds, Moser et al. (1963) p. 8.

Primary ExaminerHenry R. Jiles Assistant ExaminerS. D. Winters Attorney, Agent, or FirmPlumley & Tyner [5 7 ABSTRACT Phthalocycanine reactive dyestuffs corresponding to the formula wherein Pc represents the radical of a phthalocyanine, R and R are hydrogen, or identical or different alkyl radicals which may be cyclized and/or further substituted, or they are optionally substituted cycloalkyl, aralkyl or aryl radicals; R represents hydrogen, an alkyl radical with l-5 carbon atoms, which may be substituted by water-solubilizing or by not watersolubilizing groups, or a cycloalkyl radical; R and R are hydrogen or lower alkyl radicals; A is hydrogen or a substituent; Y is the group SO -CH Cl-I- OSO H, SO CH=CH SO Cl-I CH- SSO H; a is a number from O to 3, b is a number from O to 2, and c is a number from 1 to 4, the sum total of a, b, and c not exceeding 4. The dyestuffs of this invention are useful in dyeing wool, silk, leather, linear polyamides and particularly cellulose, containing fibrous materials such as linen, regenerated cellulose, and cotton.

9 Claims, No Drawings l WATER-SOLUBLE PHTHALOCYANINE REACTIVE DYESTUFFS CONTAINING AN ETHYLSULFONYL SUBSTITUENT The subject matter of the invention relates to new' water-soluble phthalocyanine dyestuffs which, in the form of their free acids, correspond to the formula In the above formula, Pc represents the radical of a phthalocyanine, R and R are hydrogen, or identical or different alkyl radicals which may be cyclized and/or further substituted, or they are optionally substituted cycloalkyl, aralkyl or aryl radicals; R represents hydrogen, an alkyl radical with l -5 carbon atoms, which may be substituted by water-solubilizing or by not water-solubilizing groups, or a cycloalkyl radical; R and R are hydrogen or lower alkyl radicals; A is hydrogen or a substituent; Y is the group SO CI-I --CH- --OSO I-I, SO -CH=CI-l --SO CH CH- 'SSO l-I; a is a number from O to 3, b is a number from to 2, and c is a number from 1 to 4, the sum total of a, b and c not exceeding 4.

In the dyestuffs of the formula (I), each sulphonic acid or sulphonamide group is linked in the 3- or 4- position with another benzene ring of the phthalocyanine. Suitable metals are cobalt, nickel and copper.

Optionally substituted hydrocarbon radicals R and R to be mentioned are, for example: lower alkyl radicals, such as methyl, ethyl, propyl, butyl'and amyl; substituted lower alkyl radicals are, e.g., lower hydroxyalkyl radicals, such as B-hydroxyethyl, 'y-hydroxypropyl; 8,7-dihydroxypropyl and pentahydroxyhexyl; lower carboxyalkyl radicals, such as B-carboxyethyl; lower sulphoalkyl radicals, such as B-sulphoethyl; cycloalkyl radicals, such as cyclohexyl; aralkyl radicals, such as benzyl; aryl radicals, such as phenyl and naphthyl; substituted aryl radicals, such as ethoxyphenyl, methoxyphenyl, sylphophenyl and carboxyphenyl.

Examples of the radical R are methyl, ethyl, B-hydroxyethyl, B-sulphoethyl, propyl, isopropyl, cyclohexyl and butyl radicals.

Suitable lower alkyl radicals R and R are, for example, the methyl and ethyl group. R and R preferably (sown.

(Ill) 5 R5 in which R R R A and Y have the same meaning as above,

and optionally with a compound of the formula HN (IV) in which R and R have the same meaning as already given above, and optionally treating the resultant dyestuffs with alkali and optionally adding sodium thiosulphate on the vinylsulphone dyestuffs thus obtained.

In this condensation sulphonic acid chloride groups may be converted into sulphonic acid groups by hydrolysis. The reaction of the phthalocyanine sulphonic acid chloride with the compound of the formula (III) and the compound of the formula (IV) can be carried -out in a single reaction step or in separatezgindividual steps. In general, the simultaneous reaction (provided b is to be greaterthan O) is of advantage. A compound of the formula (IV) may here serve as acid-binding agent.

By a preferred method of carrying out the process the dyestuffs according to the invention can be obtained by using amines of the general formula in which R R R and A have the same meaning as above, instead of the compounds of the formula (III), subsequently converting the resultant condensation products in known manner into the acidic sulphuric acid esters and optionally treating them with alkali and possibly adding sodium thiosulphate on to the vinylsulphone dyestuffs thus obtainable, phthalocyanine dyestuffs of the formula (I) [Y --SO CI-I CH -S-'SO I-I] thus being formed. The metal-containing phthalocyanine sulphonic acid chlorides used as starting substances according to the invention can be produced in known manner, for examtion for the condensation with the appropriate metalcontaining phthalocyanine sulphonic acid chlorides,

the following amines are, for example:

B-hydroxyethyl-[ 4-( methylaminoacetylamino phenyl -sulphone B-hydro xyethyl-[ 4-( ethylaminoacetylamino )-phenyl sulphone,

B-hydroxyethyH 3-( methylaminoacetylamino phenyl ]-sulphone,

B-hydroxyethyH 3-( methylaminoacetylamino )-4- methoxy-phenyl]-sulphone,

,B-hydroxyethyH 2,5-dimethoxy-4-( methylaminoacetylamino )-phenyl ]-sulphone,

B-hydroxyethyl-[4-methyl-3-(methylaminoacetylamino)rphenyl]-sulphone,

B-hydroxyethyH 3-(methylaminoacetylamino-4- bromo-phenyH-sulphone,

B-hydrOXyethyI-I 2,5-dichloro-4-( methylaminoacetylamino )-phenyl -sulphone,

,B;hydr oxyethyl 3-( methylaminoacetylamino )-4- hydroxyphenyl1-sulphone,

,B-hydroxye thyl- 4-( B-sulphoethylaminoacetylamino phenyl]-sulphone,

B-hydroxyethyl-[4-( B-hydroxyethylaminoacetylamino)-phenyl]-sulphone,

B-hydroxyethyl- 4-( 2-methylamino-propionylamino phenyl ]-sulphone B-hydroxyethyl-[4-(methylaminoacetylamino )-3-carboxy-phenyl1-sulphone,

B-hydroxyethyl-[4-(methylaminoacetylamino)-3-sulpho-phenyl1-sulphone. The amines of the formula (V) can be used for the 7 process according to the invention either in the form of free bases or in the form of their water-soluble salts with halogen hydracids.

Examples of amines of the formula (IV) are ammonia, ethylamine, methylamine, propylamine, taurine, N-methyltaurine, aminoacetic acid, sarcosine, ethanolamine, diethanolamine, morpholine, benzylamine, aniline, m-sulphanilic acid, p-anisidine, 4-aminobenzoic acid etc.

The reaction of the phthalocyanine sulphochlorides v of the formula (II) used, in solution or suspension and/or with the addition of acid-binding agents. For carrying out the reaction in a non-aqueous medium, organic solvents or diluents, for example, methanol, dimethyl formamide or pyridine may be considered. As acid-binding agents there may be used sodium bicarbonate, sodium carbonate, sodium hydroxide, tertiary organic bases, such as pyridine or triethylamine, or an excess of the amines of the formula (IV) employed. The reaction is carried out at weakly acidic to alkaline pH values. The reaction temperature required may vary within a wide range. As a rule, the operation is carried out between 0 and 60C.

The second process step of the preferred embodiment of the invention, i.e. the conversion of the phthalocyanine sulphonamides containing B-hydroxyethyl sulphonyl groups obtained in the first reaction step, into their acidic sulphuric acid esters by treatment with sulphonating agents is carried out in known manner by treating the sulphonamides either with sulphuric acid or by reacting them with chlorosulphonic acid or sulphur trioxide or their complexes with tertiary amines, preferably in a tertiary amine as solvent or, alternatively, in an organic solvent with the addition of amidosulphonic acid.

The new phthalocyanine dyestuffs to be obtained according to the invention can be used for the dyeing and printing of materials of the greatest variety, for example, of wool, silk, leather or linear polyamides. The new dyestuffs are particularly suitable for the dyeing and printing of cellulose-containing materials of a fibrous structure, such as linen, regenerated cellulose and especially cotton. The application of the dyestuffs on to the cellulose fibres is carried out, for example, by treating the material with an aqueous solution of the duestuff and an aqueous solution of an alkaline or acidbinding agent, such as sodium hydroxide, sodium bicarbonate, trisodium phosphate or sodium sulphide, or by a treatment with a printing paste containing the dyestuff as well as an acid-binding agent. The dyestuff solutions or printing pastes may contain, besides acidbinding agents or substances yielding such substances, urea, urethanes, or water-soluble amides of aliphatic carboxylic acids, for example, formamide, acetamide or malonic acid diamide. The treatment with the acidbinding agents may be carried out before, during or after application of the dyestuff, if desired, at an elevated temperature. 7

The dyestuffs obtainable according to the invention yield on the afore-mentioned materials dyeings and prints of pure blue to green shades which are characterised by good fastness to light, good fastness to chlorine and generally by very good fastness to wet processing.

The parts in the following Examples stand for parts by weight; the temperatures are given in degrees centigrade.

EXAMPLE 1 96 Parts of the copper phthalocyanine tetrasulphochloride obtained in usual manner by an aftertreatment with thionylchloride are suspended in 2000 parts ice-water and the suspension is neutralised with a caustic soda solution. 62 Parts of the hydrochloride of 3-hydroxyethyl-[4-methylaminoacetylamino phenyl]-sulphone in the form of an aqueous solution are subsequently added. The mixture is heated to 40 and the pH maintained between 9 and 10 by the dropwise addition of a caustic soda solution. The condensa- 6 tion is completed whenycaustic soda solution is no B-hydroxyethyl-[4-( B-hydroxyelonger consumed. The dyestuff is quantitatively precipthylaminoacetylamino)-phenyl]-sulphone, itated by the addition of a little sodium chloride and B-hydroxyethyl-[4-(B-sulphoethylaminoacetylamino)- isolated by suction-filtration. After the drying at 100, phenyl]-sulphone, the finely ground product is introduced into 1000 parts 5 B-hydroxyethyl-[4-(ethylaminoacetylamino)-phenyl]- concentrated sulphuric acid and the mixture is stirred sulphone, overnight at room temperature. It is poured on to ice, B-hydroxyethyl-[4-cyclohexylaminoacetylamino)- and the precipitated dyestuff is filtered off. The moist phenyl]sulphone,

paste is stirred in 1000 parts of water and neutralised B-hydroxyethyH4-(methylamino-acetyl-N- with sodium carbonate. After salting out with sodium 10 methylamino)-phenyl]-sulphone. chloride, the product is again dried. In the form of the free sulphonic acid, the reaction product corresponds EXAMPLE 2 to the following average constitution 96 Parts of the copper phthalocyanine tetrasulpho- .1"): ([CuPc] 3O 1 '1 CH- CIi l Q- so cn cn oso m ll CH3 0 H The dyestuff is very readily soluble in water. chloride obtained in usual manner by an after- When a cellulose fabric is printed with a printing treatment with thionylchloride are slurried in 2000 paste which contains, per kilogram, 20 g of the dyeparts ice-water and the suspension is neutralised with stuff, 150 g urea, 300 ml water, 500 g alginate thickena caustic soda solution. 31 Parts of the hydrochloride ing, 20 g sodium bicarbonate and which was made up of B-hydroxyethyl-[4-(methylaminoacetylamino)- with water to l kilogram, subsequently dried, steamed phenyl]-sulphone in the form of an aqueous solution at 150 for 1 minute, rinsed with hot water and soaped are subsequently added. A pH of 9 is maintained by the at the boil, an intense turquoise-blue dyeing is Obdropwise addition of a 2N ammonia solution. The mixtained. It should be emphasized that the not fixed porture is then heated to and kept at this tempertions are readily washed out, and that the print is very ature untilammonia is no longer consumed for main- UnifOrm 0n Cotton and Staple fibre- 30 taining a constant pH. After the addition of sodium A yestuff of similar proper ies th yeing f hi h chloride the dyestuff is precipitated and dried at 100. exhibits a markedly more greenish shade is obtained Th d y dyestuff is introduced at room temperature when the pp phthalocyanine-(3)-tetrasulph0nic into 1000 parts concentrated sulphuric acid and the acid chloride is replaced by an equivalent am of mixture stirred overnight. It is then poured on to ice, nickel p h l y n p acid ChlO- 35 the product is filtered off with suction and the paste is Fide- I introduced into about 1000 parts of ice-water and neuwheh the B' y y y tralised by the careful addition of a caustic soda soluthylaminoacetylamino)-phenyl]-sulphone used in this i Example is replaced y an 6qhivaleht amount of the The dyestuff is again filtered off with suction and compounds set out in the following, valuable reactive 4O d i d I h fo f h f l h i id h d dyestuffs are likewise Obtained which also y cellulose stuff corresponds to the following average constitution:

Cup 4&3:

SO -N-CH IJII I Q SO CH CH OSO -,H

his 0 H fabrics in turquoise-blue shades. From a long bath the dyestuff yields an intense red- B-hydroxyethyH4-(methylaminoacetylamino)3- dish turquoise shade of good fastness properties.

chloro-phenyH-sulphone, A dyestuff of similar properties, the dyeings of which ,B-hydroxyethyl-[4-( methylaminoacetylamino)-3- however exhibit a markedly more greenish shade,'is obmethoxy-phenyl]-sulphone, tained when the copper phthalocyanine-(3)-tetrasul- B-hydroxyethyl-[4-(methylaminoacetylamino-3- phonic acid'chloride used is replaced by the equivalent bromo-phenyl]-sulphone, I amount of nickel-phthalocyanine-(3)-tetrasulphonic ,B-hydroxyethyH4-(methylaminoacetylamino)-3-nitroacid chloride.

phenyI]-sulphone, ,B-hydroxyethyl- [4-( methylaminoacetylamino )-3-carb EXAMPLE 3 oxy-phenyl ]-sulphone, B-hydroxyethyH4-(methylaminoacetylamino)-3-sul- 96 Parts of the copper phthalocyanine tetrasulphopho-phenyH-sulphone, chloride obtained in usual manner by an after- B-hydroxyethyl-[4-(methylaminoacetylamino)-2,5- treatment with thionylchloride are stirred in 2000 parts dichloro-phenyl]-sulphone, ice-water and the mixture is neutralised with sodium ,B-hydroxyethyl-[4-( methylaminoacetylamino )-2,5- carbonate. 31 Parts of the hydrochloride of B-hydroxydimethoxy-phenyl l-sulphone, ethyl- 4-( methylaminoacetylamino )-phenyl ]-sulphone B-hydroxyethyl-[4-(methylaminoacetylamino)-3- in the form of an aqueous solution and 9 parts morphomethyl-phenyH-sulphone, line are subsequently added at the same time. The pH B-hydroxyethyH 3-(methylaminoacetylamino)- is maintained at 9 by the dropwise addition of a caustic phenyli-sulphone, soda solution. The mixture is heated to 40, while stir- 7 8 ring, and kept at this temperature and at the pH rnen- When the instructions of this Example are followed, tioned until caustic soda solution is no longer conbut the copper phthalocyanine-(3)-trisulphochloride is sumed. By the addition of sodium chloride the dyestuff replaced by the equivalent amount of nickel phthalocyis quantitatively precipitated. After drying at 100 and anine-(3)-trisulphochloride, a valuable reactive dyegrinding, it is introduced into 1000 parts concentrated 5 stuff is likewise obtained, the dyeings of which exhibit,

sulphuric acid and the mixture stirred at room temperav however, a markedly more greenish shade.

ture overnight. The dyestuff is poured on to ice, filtered dftth'tdt"l0 off an a er e in to uc ion into parts of ice EXAMPLE water, neutralised by the careful addition of a caustic soda solution. After salting out, filtering off and drying 1O 96 Parts of the copper phthalocyanine-(3)-tetrasulat 70 in a vacuum drying cabinet, a blue dyestuff powphochloride obtained in usual manner by an afterder is obtained which dissolves in water with a blue coltreatment with thionylchloride are slurried in 2000 our. In the form of the free sulphonic acid, the dyestuff parts ice-water and the mixture is neutralised. 71 Parts corresponds to the following average constitution of the sulphuric acid semiester of B-hydroxyethyl-[4- When the instructions of Example 3 are followed, but y a y )-p y lp are the morpholine is replaced by the amines set out in the sprink d in- Th t mpe atu e i ra sed o 35 to 40, and following, valuable blue reactive dyestuffs are likewise the pH simultaneously maintain d at tw n 8-5 and obtained. The amount of the amine used is variable to 9 by he r pwi a i ion f a dium carb nat soluthe extent as indicated by the index (b): methylamine, tion. When, under the conditions mentioned, sodium dimethylamine, cyclohexylamine, benzylamine, etha- Carbonate is no longer consumed, the dyestuff is sepanolamine, diethanolamine, taurine, N-methyl-taurine, rated by the addition of sodium chloride. After filtering aminoacetic acid, sarcosine, aniline etc. off and drying, a blue dyestuff powder is obtained which dissolves in "water with a clear turquoiseblue EXAMPLE 4 colour. In the form of the free sulphonic acid, the dye- 86 Parts of the copper phthalocyanine trisulphochlostuff corresponds to the following average constitution:

ride obtained in usual manner by an after-treatment A valuable dyestuff is likewise obtained when the with thionylchloride are slurried in 2000 parts icecopper phthalocyanine tetrasulphochloride is replaced water, and the mixture is neutralised with a caustic by the corresponding amount of nickel phthalocyanine soda solution. 62 Parts of the hydrochloride of B-hydrtetrasulphochlon'de. oxyethyl-[4-(methylaminoacetylamino)-phenyl]- However, the shade obtained with this product is sulphone are subsequently added in the form of an markedly more greenish.

aqueous solution. The mixture is heated to 40 and the I claim:

pI-I maintained at 9 by the dropwise addition of a causl. A phthalocyanine reactive dyestuff of the formula tic soda solution. After completion of the condensation, the dyestuff is quantitatively precipitated by the addition of sodium chloride. After drying at 100, the

finely ground dyestuff powder is introduced into 1000 parts concentrated sulphuric acid. The mixture is (so H) stirred overnight at room temperature and then poured a A on to ice. The precipitated dyestuff is filtered off, slur- P so N 1 ried in 1000 parts ice-water, and carefully neutralised. CT 2- Y The dyestuff is again filtered off with suction and dried.

, (SO NCH-CN )r In the form of the free sulphonic acid, it corresponds I I I I I to the following average constitution: R 0 R,

by good manufacturing fastness properties.

When, according to the method described following in which Pc' represents the radical of a phthalocyanine Example I, the dyestuff is printed on cotton an intense joined to theindicated substituents at ,the 3- or 4- blue turquoise shade is obtained which is characterised position of different benzene rings of the phthalocyanine nucleus; R, and R are hydrogen, or identical or 9 10 different alkyls of 1-5 carbon atoms which are unsubi hi h P d A have th meaning given in claim stitu'ted or are substituted by hydroxy, carboxy, sulfo, v 1, R, represents lower alkyl, stands for l, 2 or 'p r cyclohexyl, benzyl, P yL naphthyl, and 3, stands for l, 2 or 3, the sum total of a and c substituted phenyl and substituted naphthyl where the not exceeding substituent is lower alkoxy, carboxy, or sulfo; R stands for hydrogen or alkyl of 1-5 carbon atoms which is un- 5. The dyestuff of the formula CH 0 H substituted or substituted by hydroxy or sulfo; R and 6. The dyestuff of the formula S03}! [NiPc] Q [so,-N- ci-i, c N SO CH CH OSO H].

i II I CH3 0 H R represent hydrogen or lower alkyl radicals; A repre- 7. The dyestuff of the formula sents hydrogen, hydroxy, lower alkoxy, carboxy, sulfo, nitro, halo, or lower alkyl; Y represents a group SO- for 0, l, or 2, and c for l, 2, 3, or 4, the sum total of I II a, b, and c not exceeding 4. o

2. A phthalocyanine reactive dyestuff of the formula N... G SO -CH -CH OSO H]s (503ml, 8. The dyestuff of the formula P s02 \R2 SO -ll lCH-C-N SO -Cl-I -CH -OSO l-l),., [NPR] R! m in i2, tch? CH 0 in which PC, 11,, R R R R A, a, b and c have the 40 meaning gi en in laim 1, 9. A phthalocyanine reactive dyestuff of claim 1 3. A phthalocyanine reactive dyestuff of the formula wherein a phthalocyanine is a Copper phthalocya- SO -CH -CH .-OSO H) in which Pc, A, a, b and 0 have the meaning given in nine, a nickel phthalocyanine, or a cobalt phthalocyaclaim 1, and R represents'a lower alkyl; nine.

7 4. A phthalocyanine reactive dyestuff of the formula (SQ-lIl-Cl-h-i- 171 0 H so CH -CH -oso H) a 2 2 2 3 c 

1. A PHTHALOCYANINE REACTIVE DYESTUFF OF THE FORMULA
 2. A phthalocyanine reactive dyestuff of the formula
 3. A phthalocyanine reactive dyestuff of the formula
 4. A phthalocyanine reactive dyestuff of the formula
 5. The dyestuff of the formula
 6. The dyestuff of the formula
 7. The dyestuff of the formula
 8. The dyestuff of the formula
 9. A phthalocyanine reactive dyestuff of claim 1 wherein said phthalocyanine is a copper phthalocyanine, a nickel phthalocyanine, or a cobalt phthalocyanine. 